Fungicides and method of making same



United States FUNGICIDES AND METHOD OF MAKING SAW No Drawing.Application February 28, 1955, Serial No. 491,174

12 Claims. (Cl. 260-270) This invention relates as indicated tocompositions having fungicidal and/or fungistatic properties and hasmore particular reference to a process for solubilizing suchcompositions.

During the past decade considerable research has been conducted for thepurpose of finding new and improved fungicidal compositions. It is wellknown that the hydroxyquinolines have good fungicidal and/or fungistaticproperties, however, they are all substantially insoluble in the commonindustrial solvents and therefore have encountered considerabledifficulties in commercial applications. Due to their substantialinsolubility these aforementioned materials have poor resistance tocracking and leaching and lose their effectiveness due to poorpenetration of the material being treated.

It is therefore a principal object of our invention to pro vide a methodand means for rendering the hydroxyquinolines soluble in the commonindustrial solvents, such as, V. M. & P. naphtha, mineral spirits, fueloil, etc.

.Other objects will become apparent as the description proceeds.

To the accomplishment of the foregoing and related ends, the invention,then, comprises the features hereinafter fully described andparticularly pointed out in the claims, the following descriptionsetting forth in detail certain illustrative embodiments of theinvention, these being indicative, however, of but a few of the variousways in which the principle of the invention may be employed.

Broadly stated this invention then comprises the method of solubilizingthe hydroxyquinolines which consist in heating a hydroxyquinolinetogether with a water insoluble metal carboxylic acid soap and an alkylphenol in which the alkyl group has at least 8 and not more than 15carbon atoms.

The alkyl radicals of the alkyl phenols, used as reactants in thepresent invention, may be normal or branched. In the case of dialkylcompounds the two alkyl radicals are not necessarily similar. We havefound the following alkyl phenols to be particularly useful in theprocess of our invention:

Octyl phenol Nonyl phenol Dodecyl phenol Penta-decyl phenol The metalsoaps which are usedas reactants in the present invention are the waterinsoluble soaps. Thus they may be soaps of any metal or mixture ofmetals which form water insoluble soaps with soap-forming acids ormixtures of such acids. In the preferred embodiment of our invention weuse the copper, zinc and nickel soaps. However, it will be noted thataluminum, magnesium and the alkaline earth metals are also usable in theinvention.

The soap-forming acids used in forming the aforementioned metal soapsinclude stearic, palmitic, lauric, Z-ethylhexoic, linoleic, linolenic,oleic, ricinoleic and naphthenic and mixtures thereof. Soap-formingfatty acids such as tall oil, rosin oil, rosin and abietic may also beused in making the water-insoluble soaps. In the preferred ematentbodiment of our invention we use those saturated and unsaturatedaliphatic acids having from 8-18 carbon atoms.

As prevously stated the hydroxyquinolines are substantially insoluble inthe common organic solvents. The reaction products of the presentinvention, on the other hand, are readily soluble in toluene, mineralspirits, naphtha, fuel oil, etc. and the resultant solutions have veryeffective fungicidal properties.

While the hydroxyquinolines in general have effective fungicidalproperties we prefer the use of 8-hydroxyquinoline.

In carrying out the process of the present invention the reactantsshould be heated to a temperature in the range of about 200 F. to thelowest decomposition temperature of the components, with good agitation.From 5% to above 20% of hydroxyquinoline can be put into solu- 158 lbs.of copper naphthenate were heated with 51 lbs. of pentadecyl phenol and27.5 lbs of S-hydroxyquinoline in an open vessel, with constantagitation, to 375 F. The temperature was held for about 15 minutes. Thesolution was then allowed to cool to about 220 F. and was then dilutedwith 82.5 lbs, of mineral spirits.

The resulting solution was brilliant, clear and substantially free ofundissolved matter when observed by the eye under a light.

The reaction products of the present invention vary at room temperaturefrom free flowing masses to solids. However, all are readily soluble andmay be diluted with any of the common solvents such as mineral spirits.Generally the reaction products of the present invention can be dilutedwith the common organic solvents at room temperature, however, we havefound that the use of heat will facilitate dispersion.

The products of the present invention may be applied in the material tobe treated by dipping, spraying or by being incorporated into a stillmore complex composition and knifed onto the material. Theaforementioned complex compositions may be of a wide variety of resinsand waterproofing agents.

200 lbs. of nickel Z-ethyl hexoate were heated with 102 lbs. of nonylphenol and 55 lbs. of 8-hydroxyquinoline in an open vessel, withconstant agitation, to about 325 F. The temperature was held for about20 minutes and allowed to cool to about 175 F. and was then: dilutedwith 280 lbs. of mineral spirits.

The resultant produce was clear when viewed with the eye under light. 7

The reaction products of the present invention may be used as fungicidaland/or fungistatic compositions in the hot liquefied state or in thesolidified state or as hot or cold solutions in the common organicsolvents.

III

310 lbs. of zinc naphthenate were heated with l02'lbs. of dodecyl phenoland 55 lbs. of 8-hydroxyquinoline in an open vessel with stirring andthe temperature was raised to about 325 F. held for about 25 minutes.The mass was allowed to cool to about 175 F. and was then diluted withlbs. of mineral spirits.

200 lbs. of copper 2-ethyl hexoate were heated with 102 lbs. of octylphenol and 55 lbs. of 8-hydroxyquincline in an open vessel with constantstirring. The temperature was raised to about 350 F. and held for about15 minutes. The mass was allowed to cool to about 225 F. and was thendiluted with 280 lbs. of mineral spirits.

The resultant product showed exceptionally good clarity andsubstantially no undissolved matter when viewed under light.

245 lbs. of copper Z-ethyl butoxy propionate were heated with 102 lbs.of dodecyl phenol and 55 lbs. of 8-hydroxyquinoline in an open vesselwith constant agitation. The temperature was raised to about 315 F. andheld for about 15 minutes. The mass was allowed to cool to about 225 F.and was then diluted with 235 lbs. of mineral spirits.

130 lbs. of nickel 2-ethyl hexoate were heated with 70 lbs. of copper2-ethyl hexoate, 102 lbs. of pentadecyl phenol and 55 lbs. of8hydroxyquinoline in an open vessel with stirring. The temperature wasraised to about 350 F. and held for about 20 minutes. The mass wasallowed to cool to about 200 F. and was then diluted with 280 lbs. ofmineral spirits.

The resultant product showed excellent clarity and excellent fungicidalproperties.

Additional reaction products of the present invention were made andtested to determine their efficacy as fungicides. Solutions of each wereused to impregnate samples of duck and they showed results substantiallyidentical with the foregoing examples.

Tests were carried out on the products of the present invention todetermine their efficacy as fungicides. Tests were as follows:

Samples of 10 oz. duck were cut 1% x 6" and the width was ravelled to1". Half of the samples were cut parallel to the filling threads.Untreated specimens were always included in the tests as controls toverify the viability of the test organisms.

The samples to be treated were dipped into a solution of one of theproducts of the present invention. As for example, the reaction productof Example I was diluted to 18.5% with mineral spirits and the textileswere dipped into this solution for 1 minute. The treated textiles werethen put through a wringer and adjusted to 65% pick up of the fungicideon a dry weight basis and then they were allowed to air dry to constantweight. One-half of the treated samples were placed directly in thefungus growth and the other half were thoroughly leached in water anddried before being subjected to the fungus growth.

Spore suspensions of chaetomium globosum and aspergillus niger wereintroduced onto an agar culture medium contained in a sterile bottle andthen incubated for 48 hours at 84- -2 F. at 90-95% relative humidity. Atthe end of the 48 hour incubation period the treated samples (leachedand unleached) and the untreated samples were dipped in distilled waterand then pressed firmly on the surface of the innoculated culture mediumto insure good contact. After 14 days the samples were observed visuallyand subjected to breaking tests.

At the end of 14 days all untreated samples were completely covered withfungi growth and were reduced in tensile strength by 50% or more. Thetreated samples both leached and unleached showed no fungus growth andsubstantially no loss in tensile strength. There was no difference inappearance between the leached and unleached treated samples, however,the leached samples showed a slightly higher tensile strength than didthe unleached samples.

The products of the present invention are stable for long periods oftime and not only inhibit the growth of fungibut also kill the activityof existing growth on contact.

Other modes of applying the principle of the invention may be employed,change being made as regards the details described, provided thefeatures stated in any of the following claims or the equivalent of suchbe employed.

We, therefore, particularly point out and distinctly claim as ourinvention: 1

1. The method of producing a composition of matter which consists ofreacting at temperatures between 200 F. and the lowest decompositiontemperature of the reactants, hydroxyquinoline, with at least one waterinsoluble metal organic acid soap, said metal soap selected from thegroup consisting of the metal water insoluble soaps of stearic,palmitic, lauric, 2-ethyl-hexoic, linoleic, linolenic, oleic,ricinoleic, naphthenic, tall oil, rosin oil, rosin and abietic acids andan alkyl phenol in which the alkyl group has at least 8 and not morethan 15 carbon atoms.

2. The method of producing a composition of matter which consists ofreacting at temperatures between 200 F. and the lowest decompositiontemperature of the reactants, S-hydroxyquinoline, with at least onewater insoluble metal organic acid soap, said metal soap selected fromthe group consisting of the metal water insoluble soaps of stearic,palmitic, lauric, Z-ethyI-hexoic, linoleic, linolenic, oleic,ricinoleic, naphthenic, tall oil, rosin oil, rosin and abietic acids andan alkyl phenol in which the alkyl group has at least 8 and not morethan 15 carbon atoms.

3. A method of producing a composition of matter which consists ofreacting at temperatures between 200 F. and the lowest decompositiontemperature of the reactants, 8-hydroxyquinoline, copper napththenateand pentadecyl phenol.

4. A method of producing a composition of matter which consists ofreacting at temperatures between 200 F. and the lowest decompositiontemperature of the reactants, 8-hydroxyquinoline, copper laurate andpentadecyl phenol.

5. A method of producing a composition of matter which consists ofreacting at temperatures between 200 F. and the lowest decompositiontemperature of the reactants, 8-hydroxyquinoline, nickel 2-ethyl hexoateand pentadecyl phenol.

6. A method of producing a composition of matter which consists ofreacting at temperatures between 200 F. and the lowest decompositiontemperature of the reactants, S-hydroxyquinoline, zinc laurate andpentadecyl phenol.

7. As a new composition of matter the product produced by claim 1.

8. As a new composition of matter produced by claim 2.

the product 9. As a new composition of matter the product produced byclaim 3.

10. As a new composition of matter the product produced by claim 4.

11. As a new composition of matter the product produced by claim 5.

12. As a new composition of matter the product produced by claim 6.

No references cited.

1. THE METHOD OF PRODUCING A COMPOSITION OF MATTER WHICH CONSISTS OFREACTING AT TEMPERATURES BETWEEN 200* F. AND THE LOWEST DECOMPOSITIONTEMPERATURE OF THE REACTANTS, HYDROXYQUINOLINE, WITH AT LEAST ONE WATERINSOLUBLE METAL ORGANIC ACID SOAP, SAID METAL SOAP SELECTED FROM THEGROUP CONSISTING OF THE METAL WATER INSOLUBLE SOAPS OF STEARIC PALMITIC,LAURIC, 2-ETHYL-HEXOIC, LINOLENIC, OLEIC RICINOLEIC, NAPHTHENIC, TALLOIL, ROSIN OIL, AND ABIETIC ACIDS AND AN ALKYL PHENOL IN WHICH THE ALKYLGROUP HAS AT LEAST 8 AND NOT MORE THAN 15 CARBON ATOMS.
 7. AS A NEWCOMPOSITION OF MATTER THE PRODUCT PRODUCED BY CLAIM 1.